Liquid catalyst paraffin alkylation process



United tates Patent '2,943,12 LIQUID CATALYST PARAFFIN ALKYLATION- PROCESS v .1

Alan Schriesheim, Fords, N.J., assignor to EssoResearch and Engineering Company, a corporation of Delaware Filed Sept. 26, 19ss,'ser. No. 163,492 1 Claims. c1; 260-68353) This invention concerns a process in which butanes and/or pentanes are alkylated with a higher .paraflin'hydrocarbon to furnish branched chain parafldn hydrocarbons boiling in the motor fuel range. In particular the invention concerns a process in which a liquid catalyst complex comprising aluminum bromide and bromine is employed to elfect a simultaneous cracking, isomerization and alkylation reaction involving isobutane and/or isopentane and a paraflin hydrocarbon of from 6 to' 18 carbon atoms under conditions that favor the formation of high yields of branched chain paraffin hydrocarbons of 5 to 7- carbon atoms. m

With the increased use of modern high compression engines in the automotive industry the petroleum refiners have; encountered amajor problem in supplying a sufiicient quantity of'motor fuels of high' octane ratiri'gto satisfy of gasoline fcomponentshas been augmented'by using'C- the requirements of thoseeiigihes. Heretofor'e the supply and C 'petroleumfractionsas starting materials for mak 'in'g' higher hydrocarbons principally by" polymerization and alkylation, processes. Thus for example, isobutane can be reacted with butyleneinthe presence of sulfuric acid to give a branched chain B-carbon-atom alkylate. Also butylene can be polymerized to a C unsaturated hydrocarbon whichupon hydrogenation will give isooctane.

that they necessitate the use of olefins which are usually in relatively limited supply.

It has now been found that bu-tanes and pentanes can 'be reacted directly with higher paraffin hydrocarbons to give good yields of C to C saturated branched'chain is in the liquid state and can be readily separated from the reaction products and recycled to the reaction zone. The catalyst exhibits markedly greater activity than the catalysts previously proposed for conducting reactions of this type. Reaction temperatures are relatively low and range from about 30 to 140 F. The pressures'employed are sufficient to keep the reacting hydrocarbons in the liquid phase. The preferred temperature range is from about to about 120 F.

The nature and objects of this invention will be more easily understood when reference is made to the accompanying drawing in which the single figure is a schematic flow plan of one process for practicing the invention.

The process will be described with particular refer ence to the use of isobutane as the lighter component. Referring now to the drawing in detail, isobutane from a suitable source is conducted by means of line 11 into a stirred reaction zone '15 containing a liquid catalyst complex comprising aluminum bromide in admixture with a halogen from the class of chlorine and bromine. A portion of the isobutane stream may be diverted by means of lines 11a and 11b through an aluminum bromide pick up vessel 12 for for the purpose of replacingalumi- These processes have some disadvantages in' that they require a number of separate operations and in num bromide that may be lost from the system by lution in the product stream. a

A stream of a higher paraflin hydrocarbon, as for example, heptane, octane, or cetane, or of mixtures containing the higher paraffins, is conducted intothe re- I action zone by means of line 16. Make-up bromine may I line 17 and is conducted into an initial separation zone 20 wherein separation of the liquid catalyst from the reaction product takes place. The settled catalyst layer may be recycled to the reaction zone by means of line 22. Light materials including unreacted isobutane and n-butane are removed overhead by means of line 21 and recycled to the reaction zone. The remainder of the reaction products may then be conducted by means of line 23 into a second separation zone 24, if necessary, for further separation of liquid catalyst from the hydrocarbons. Line 24 may comprise a centrifuge, for example. Separated catalyst is added to that in line "22. by means of line 25. .The

essentiallycatalyst-free product is sent via line 26 to a product separation zone 28,; wherein various fractions including C to O hydrocarbons may be removed overbutane will be recycled throughline 17,zone 20 and line 21 until a considerable amount'of the butane; has been isomerized to isobutane. The process inay't-hen continue in the manner :already' described, the recycle isobutane being sufficient to makethe reaction proceed, while the fresh butane becomes isomerized in the reactionzone;

A number of factors in the process of the present invention are critical to its operation in order that-proper distribution of the products may be obtained: For ex- 1 ample, at temperatures above about 140 F. considerable cracking occursand the principal products arepropane and lighter materials. Also it has been established that r V 7 aluminum bromide alone or even in the presence of conventional hydrogen halide promoters such as hydrogen bromide is very much less active than the catalyst systern of the present invention. On the other hand, how- 7 ever, hydrogen bromide may be employed along with the catalyst complexes of the present invention for: even greater activity. 7 i

The catalyst complexes of this invention are prepared from mixtures of from about 20 to 100 parts of-b-romine per 100 parts of aluminum bromide. The preferred range is from 25 to weight percent of chlorine or bromine based on the AlBr The catalyst complex with bromine may be prepared by mixing the aluminum the halogen exterior of the reaction zone. Alternatively either of the complexes may be prepared in the reaction zone by placing a charge of aluminum bromide in the zone and conducting in the required quantity of bromine i or chlorine with a portion of the hydrocarbonfeedQ. 7

As a minimum it is preferred that the mole ratio =o isobutane to higher paraffin in the reaction zone be at least 3 to 1. If sufiicient iso-C; is not present in the reaction zone to effect alkylation of the materials obtained when a higher paraffin or other higher product of the reaction is cracked by the catalyst, catalyst sludging will result. Mole ratios as high as 10 to 1 may be empolyed.

The feed stock must be essentially free of aromatic hy- I drocarbons and not more than about 0.02% of such ma- Patented June28, 1960 bromide with terialshould be present. An added advantage is that naphthenehydrocarbons may be tolerated in thefeed stock up to about 20 volume percent. With increased naphthene content the reaction severity-must be increased somewhat asioomparedrm a reaction inthe absence of-naphthenesi This may be accomplished by raising the temperature and/or by lowering the feed; rate, for example;

To remove aromatics from thefeed stock conventional techniques may be employed such as solvent extration; hydrogenation, acid treating and the like, as well as treatment withselective adsorbents suchas molecular sieve zeolites. It is not necessary: that thehigher hydrocarbons used be individual hydrocarbons such as heptaneror-octane or cetane, for example, but mixtures may beused, such as a petroleum fraction containing paraflinic hydrocarbons in the range of 6 to 18 carbon atoms.

Feed rates: may. vary from about 0.2 to about 2 v./v./hour but are prefer-ably in the range of about 0.3 to about 1 v./v ./hour.

The following example illustrates the practice of the present invention and points up the advantages thereof.

at' 68 to 72 F. with 23.6 grams of aluminum bromide alone or. with one of. the promoters identified in Table I. At theend'of each runthe yieldof products was determined; the results.- ohtained are. also shown. in Table I.

Table].

'resta =Iest2 Test3 'Ifest4 Catal st ems:

than? 23. 6 23. 6 23. e 23. HBr 24.0 Bromine Y 9 11.8

Analysts of'CQ-F Product; Weight" P nt:

ixo... 0.4, 0. s 21. 0 44. 4 11-05.... i 0.3 as r 2.3 as "r nting"; 0.7 4.1' 23.3 51.2

iso-C; 0. s 0; a 10. 2 25. 0 11-0,- 0 0v 0.4 1.0

TotalG' 0.5 0.3 10.6 20.0

i5o C 4s. 2 4s. a a1. 3 14. 4 11-01 52.0 47.3 34.4 8.4

Total 01 as. s 95.6 05.1 22.8

Itwill be. seen from the results. ofthese tests that aluminum bromide alone or even in the presence. of hydrogen bromide, which is a well known promoter for aluminum bromide, was not effective in producing the desired reaction. In both Test 1 and Test 2 the major portion of the reaction products comprised C hydrocarbon isomers. Thus aluminum bromide alone or promoted with hydrogen bromide acted principally as an isomerization catalyst for the. n-heptane. On the other hand, in the tests in which bromine was employed as the promoter, high yields of C and C branched-chain isomers were obtained. The bromine formed a liquid complex with the aluminum bromide, the complex being present as a readily separable second phase in. the reaction mixture.

It is not intended that the scope of this invention be limited'tothe specific examplespresented'. as. modifications thereof within the confines offthe invention as defined by the appended. claims are alsocontemplated.

What isclaimedisr 1. A process for the preparation of high octane naphtha components consisting largely of branched chain paraffin hydrocarbons of 5 to 7 carbon atoms. which comprises contacting in a reaction zone a minor proportion of a straight chain parafiin hydrocarbon of from 6 to 18 carbon atoms with a major proportion of a lighter hydrocarbon selected from thegroup consistingof butanes and pentanes, at temperatures no higher than about 140 F., in. the presence of a catalyst complex comprising aluminum bromide promoted with from 20 to weight per, cent of ahalogen. selected from the group consisting of elemental bromine and. elemental chlorine.

2. Process as defined by claim 1 wherein said catalyst comprises aluminum bromide and from about 25 to about 75 weight percent of bromine based on the aluminum bromide.

3 Process asdefined by claim 1 whereinthe temperature of the reaction is in the range of about 50 to about 12.0? F.

4. Process. as defined. by claim. I conducted in. the presence ofhydrogen bromide. as a.promoter.

5.. Process as defined. by claim 1 wherein naphthenic hydrocarbons are presentwith said hydrocarbons of from 61to.18earbon atoms.

, 6. Process as defined by claim 1 wherein the mol ratio of said lighter hydrocarbon selected from the group con sisting of butanes and pentanes to said hydrocarbonof from. 6 to 18. carbon'atoms in the reaction zone is in. the range of from about 3 to 1 to about 10 to 1.

7. A process for the preparation of high octane naphtha components. consisting. principally of branched chain parafiin. hydrocarbons of from 5 to 7 carbonatoms which comprises reacting amajor proportion ofisobutane with alminor. proportion. ofheptane, in the liquid phase, at temperatures no higher than about F., in the presence of a liquid catalyst complex comprising aluminum bromide and from about 25 to about 75 weight percent of elemental bromine, based onv the aluminum bromide.

References Cited in the fileof this. patent UNITED STATES PATENTS 2,280,748' Calhoun Apr. 21, 1942 2,349,458 Owen et a1. May 23, 1944 2,369,444 DOuville et a1. Feb. 13, 1945 Burk Feb. 27, 1945 

1. A PROCESS FOR THE PREPARING OF HIGH OCTANE NAPHTHA COMPONENTS CONSISTING LARGELY OF BRANCHED CHAIN PARAFFIN HYDROCARBONS OF 5 TO 7 CARBON ATOMS WHICH COMPRISES CONTACTING IN A REACTION ZONE A MINOR PROPORTION OF A STRAIGHT CHAIN PARAFFIN HYDROCARBON OF FROM 6 TO 18 CARBON ATOMS WITH A MINOR PROPORTION OF A LIGHTER HYDROCARBON SELECTED FROM THE GROUP CONSISTING OF BUTANES AND PENTANES, AT TEMPERATURES NO HIGHER THAN ABOUT 140*F., IN THE PRESENCE OF A CATALYST COMPLEX COMPRISING ALUMINUM BROMIDE PROMOTED WITH FROM 20 TO 100 WEIGHT PERCENT OF A HALOGEN SELECTED FROM THE GROUP CONSISTING OF ELEMENTAL BROMINE AND ELEMENTAL CHLORINE. 